Generation of Carbon Radical from Iron |
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Generation of Carbon Radical from Iron
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Iron-hydride and alkene constitute a promising pair of reactants to access alkyl carbon radicals. However, the fundamental mechanistic scenario remains unclear. High-level coupled cluster calculations reported in this work demonstrate that for iron(III)-hydrides, hydrogen atom transfer (HAT) is favored over hydrometalation. The oxidation state of iron makes a remarkable difference in the reactivity of the iron-hydride such that ferric FeIII–H is much more reactive in HAT than ferrous FeII–H. Akin to iron(IV)-oxo, exchange-enhanced reactivity (EER) dictates the intrinsic spin HAT reactivity of iron(III)-hydride. However, it is not two-state reactivity (TSR) but single-state reactivity (SSR) that operates in HAT with iron(III)-hydride. The reactivity insights gained herein for alkyl liberation from iron-alkyls may have profound mechanistic implications on the iron-dependent bioorganometallic radical chemistry in radical SAM enzymes.
中文翻译：
氢化铁和烯烃构成了有希望的一对反应物，用于进入烷基碳原子团。但是，基本的机械方案仍然不清楚。这项工作中报告的高级耦合簇计算表明，对于氢化铁（III），氢原子转移（HAT）优于加氢金属化。铁的氧化态在氢化铁的反应性上产生了显着差异，因此，Fe III -H铁在HAT中的反应性比亚铁Fe II高得多。-H。类似于铁（IV）-氧代，交换增强反应性（EER）决定了氢化铁（III）的固有自旋HAT反应性。但是，在HAT中与氢化铁（III）一起运行的不是两态反应性（TSR），而是单态反应性（SSR）。本文获得的从铁-烷基释放烷基的反应性见解可能对自由基SAM酶中铁依赖性生物有机金属自由基化学有深远的机械影响。 |
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